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    • 专利摘要:
    The invention relates to a method useful for monitoring the progress of the melting during the production of a silicon ingot by germ - directed solidification, comprising at least the steps of: (i) disposing, in a crucible a silicon charge positioned on the surface of one or more silicon seeds; said one or more seeds, and / or said silicon charge in one or more given position (s), comprising one or more tracer agents chosen from n-type or p-type doping agents having a partition coefficient in the silicon less than or equal to 10-1; metal elements having a partition coefficient in silicon less than or equal to 10-4; and the iso-electronic elements of silicon germanium and tin; (ii) evaluating, during the melting of the silicon charge, the presence and / or amount of tracer agent (s) by a chemical measurement technique of the LIBS type on the surface of the molten silicon bath; and (iii) determining, from the LIBS measurement (s), the progress of the merger.
    公开号:FR3059013A1
    申请号:FR1661209
    申请日:2016-11-18
    公开日:2018-05-25
    发明作者:Etienne Pihan；Malek BENMANSOUR；Loic Patatut
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER OF ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment.
    Extension request (s)
    Agent (s): NONY CABINET.
    MONITORING THE PROGRESS OF THE MERGER BY LIBS TECHNIQUE DURING THE DEVELOPMENT OF A LINGOT BY SOLIDIFICATION DIRECTED BY RESUMPTION ON GERMES.
    FR 3,059,013 - A1 (5f) The invention relates to a method useful for monitoring the progress of the fusion during the preparation of a silicon ingot by solidification directed by recovery on seeds, comprising at least the steps consisting of :
    (i) dispose, in a crucible, of a silicon charge positioned on the surface of one or more silicon nuclei;
    the said seed (s), and / or the said silicon charge in one or more given position (s), comprising one or more tracer agents chosen from n-type or p-type doping agents having a partition coefficient in the silicon less than or equal to 10 * 1 * * ; the metallic elements having a partition coefficient in silicon less than or equal to 10 '4; and the iso-electronic elements of silicon germanium and tin;
    (ii) assessing, during the melting of the silicon charge, the presence and / or the amount of tracer agent (s) by a chemical measurement technique of LIBS type on the surface of the molten silicon bath; and (iii) determine, from the LIBS measure (s), the progress of the merger.
    i
    The present invention relates to a new process for monitoring the progress of a cycle for developing a silicon ingot by solidification directed by recovery on seeds, more particularly useful for the detection of the end of fusion.
    Silicon ingots are conventionally produced by melting a silicon filler, followed by the directed crystallization of silicon. This directed solidification technique advantageously makes it possible to crystallize large volumes of silicon, and to adjust the size of the machined ingots by varying the dimensions of the crucibles.
    More specifically, the development of a silicon ingot by taking up germs in a directed solidification furnace implements the following steps.
    A germ or paving of silicon germs, of known thickness, is positioned at the bottom of a crucible, generally made of silica, graphite or the like. A quantity of solid silicon, called "charge", is then placed in the crucible.
    Directed melting is triggered by the oven heating program. The fusion propagates from the top to the bottom of the load, which results in a gradual approximation of the solid / liquid interface of the said germ (s) lining the bottom of the crucible.
    When the silicon is completely molten, and the germs start to melt, the silicon is solidified, in a directed manner, at low speed (typically 5 to 30 mm per hour).
    The success of the recovery on germs depends on the knowledge of the position of the solid / liquid interface, in particular on the exact prediction of the position of stop of the fusion. Indeed, it is essential to control the stop position of the fusion, so as to avoid the total dissolution of the germ (s), the initiation of crystallization being possible only if the molten bath is in contact with germs which have remained at least partly solid.
    As such, it is particularly crucial to know the progress of the solid / liquid interface, in particular its position at the end of fusion, before the initiation of solidification.
    Currently, the detection of the end of fusion is generally carried out by a mechanical probing operation using a quartz rod. This mechanical probing provides information on the position of the solid / liquid interface during fusion. Information on the position of the solid / liquid interface makes it possible to trigger the transition from the melting program to the crystallization program of the furnace at the desired time.
    However, this method of detection by probing, in addition to being expensive, is an intrusive technique. It induces in particular a risk of contamination of the silicon during probing, in particular by the quartz of the cane used.
    This method (manual or possibly mechanically automated) also requires taking an initial reference of the position of the surface of the seeds with respect to a furnace reference (“zero” dimension) and induces an uncertainty of measurement of the position of the interface. non-negligible solid / liquid.
    To avoid such an intrusive probing step during the directed solidification process of the ingot, it has already been proposed to carry out an indirect and contactless measurement of this solid / liquid interface, by knowing the position of the gas interface. /liquid. One can for example quote the document DE 102 34 250 which proposes to follow the progress of the crystallization of a medium, in particular of silicon, by measurement of the evolution of the volume of the medium during the crystallization, for example by measurement optical.
    The present invention aims to propose a new method for monitoring the advance of the melting front, making it possible to overcome the intrusive operation of mechanical probing of the solid / liquid interface.
    More specifically, the invention relates, according to a first of its aspects, to a method useful for monitoring the progress of the fusion during the preparation of a silicon ingot by solidification directed by recovery on seeds, comprising at least the steps consisting of:
    (i) have, in a crucible, a silicon charge positioned on the surface of one or more silicon nuclei;
    said seed (s), and / or said silicon charge in one or more given position (s), comprising one or more elements, called tracer agents, chosen from:
    . n-type or p-type doping agents having a partition coefficient in silicon less than or equal to 10 ′ 1 ;
    . the metallic elements having a partition coefficient in silicon less than or equal to 10 '4; and. the iso-electronic elements of silicon, specifically tin (Sn) and germanium (Ge);
    (ii) assess, during the melting of the silicon charge, the presence and / or the amount of tracer agent (s) by a chemical measurement technique of laser induced plasma spectroscopy (LIBS) type, on the surface of the molten silicon bath; and (iii) determine, from the LIBS measure (s), the progress of the merger.
    The term “advancement of the fusion” is understood more particularly to mean the position of the interface solid silicon / liquid silicon (or molten), also called “melting front” in the crucible during the melting of the silicon charge during a cycle for developing a silicon ingot by taking up germs in a directed solidification oven.
    The tracer agents used according to the invention to identify the position of the melting front are referred to more simply in the remainder of the text under the designation "tracers".
    The method according to the invention thus takes advantage of a technique of non-intrusive chemical analysis of spectroscopy type on a laser-induced plasma (also called "LIBS" for "Laser Induced Breakdown Spectroscopy" in English) of the liquid bath, for know the progress of the melting front.
    The LIBS technique advantageously allows an in situ analysis of the composition of the molten silicon bath, without requiring sampling or contact, as well as a speed of information acquisition.
    The LIBS technique is a well-known physical analytical method, typically used to allow rapid, direct (without preparation of samples) and online analysis of materials in solid, liquid or gaseous form.
    It uses laser ablation of a material to create a plasma, then spectroscopic technology for the observation and analysis of the plasma light spectrum to determine the components of the material.
    More specifically, the LIBS technique involves focusing a laser pulse towards the surface of a sample of the material to be analyzed, which causes the formation of a micro-plasma. This micro-plasma is formed almost immediately, that is to say when the laser pulse is not finished. At the end of the laser pulse, the atomic and ionic species of the micro-plasma de-energize and then re-emit radiation which an analyzer, ie a spectrometer, captures and translates in order to obtain a spectrum describing the chemical species which made up l 'sample.
    Thus, the LIBS technique can allow the identification, thanks to the emission wavelength, and the quantification, thanks to the emission intensity, of the components present in the material to be analyzed. In addition, the LIBS technique making it possible to perform a remote analysis, it proves to be particularly suitable for the analysis of materials in the molten state at high temperature, and in particular for the analysis of molten silicon, and the analysis of materials that cannot be handled because they represent a potential danger. Also, in the case of molten metals, such as silicon, the LIBS technique is capable of providing real-time changes in the chemical composition of the material.
    Analysis by LIBS has already been proposed in documents WO 2004/001394 and WO 2015/177223 for the analysis of a molten metal, for example silicon, in order for example to allow continuous monitoring of the concentrations of impurities in molten metal during a metal purification process.
    To the knowledge of the inventors, the LIBS technique has however never been implemented, in association with the voluntary incorporation into silicon of one or more tracers as defined above, in order to know the progress of the fusion in a cycle development of an ingot by solidification directed by recovery on germs.
    In the context of the process of the invention, the LIBS technique, combined with the incorporation of one or more tracers in the filler and / or the seeds, makes it possible to identify the presence in the bath of molten silicon, or even the concentration, in tracers, and therefore the moment when the melting front reaches the position of said tracer (s).
    The LIBS technique allows detection levels of the order of ppm by weight for the tracer agents used according to the invention, in line with the applications envisaged for the silicon ingot, as detailed in the following text.
    The method according to the invention advantageously makes it possible to dispense with the intrusive probing method.
    In addition, it makes it possible to determine the position of the melting front, in particular the end of fusion, with a reduced measurement uncertainty compared to the probing method. Finally, it has good reproducibility.
    According to another of its aspects, the invention thus relates to the use of the method according to the invention, for detecting the end of fusion of a cycle for the production of an ingot by solidification directed by recovery from germs, and in particular to automate the stopping of the melting program of the directed solidification furnace.
    Other characteristics, variants and advantages of the method according to the invention, and of its implementation for automating the fm of fusion, will emerge more clearly on reading the description, examples and figures which follow, given by way of illustration and non-limiting of the invention.
    In the following text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and are intended to mean that the terminals are included, unless otherwise stated.
    Unless otherwise indicated, the expression "comprising / comprising a" must be understood as "comprising / comprising at least one".
    As mentioned above, the method of the invention is implemented to monitor the progress of the fusion during a cycle for developing a silicon ingot by taking up seeds in a conventional directed solidification device.
    In general, and not detailed in the rest of the text, the production of a silicon ingot by directed solidification is carried out in a directional solidification furnace.
    It includes the positioning of one or more germs at the bottom of a crucible, for example a silica or graphite crucible, possibly covered with a layer of SiC. The crucibles are known to withstand heating at high temperatures suitable for obtaining the liquid bath.
    The seeds can for example be of a straight paved shape, of square and rectangular base, and form a paving at the bottom of the crucible in the form of a regular grid. They generally have a thickness of between 10 and 40 mm, so as to have a certain room for maneuver in the partial fusion of the seeds at the start of the solidification phase.
    It is the general knowledge of those skilled in the art to adequately adapt the means and operating conditions of the directional solidification furnace used.
    The furnace used can be a conventional directed solidification furnace, such as for example a crystallization furnace of the HEM type (from the English name "Heat Exchange Method") or of the Bridgman type with a fixed heating from the top and the sides.
    Generally, the displacement of the solid / liquid interface in the crucible comes from the modulation of the heat delivered and the heat extracted in the different parts of the crucible. Different means of heating (eg resistive or inductive) or heat extraction can be used.
    TRACING AGENTS
    As mentioned above, one or more tracer agents are integrated according to the invention at the level of the silicon charge and / or of the silicon seeds used for the preparation of the silicon ingot by directed solidification.
    It is understood that, insofar as the tracer agents are found, at least in part, in the molten silicon bath, at the end of the fusion of the silicon charge and partial fusion of the seeds, their nature and quantity put implemented are adjusted so as to obtain, at the end of the directed solidification, the properties, in particular in terms of doping (for example of n type or of p type) and of resistivity, desired for the final ingot.
    The term “final ingot” denotes, in the remainder of the text, the ingot obtained at the end of the directed solidification cycle, in other words the ingot solidified from the molten charge of silicon.
    In fact, it is known that the addition of an impurity in a silicon ingot can have an influence on the electronic quality, on the resistivity and / or on the lifetime of the charge carriers.
    On the other hand, it is conventional to dop the silicon charge to control the electrical properties of the resulting silicon ingot. In fact, the contents of p-type and n-type dopants, typically boron and phosphorus, govern the resistivity of the silicon.
    The nature and the contents used in tracer agents according to the invention are chosen in an appropriate manner in consideration of the desired final ingot.
    More particularly, the tracer agents according to the invention can be chosen from:
    - n-type or p-type doping agents having a partition coefficient in silicon less than or equal to 10 '1;
    - metal elements with a very low partition coefficient in silicon, in particular less than or equal to 10 '4; and
    - the iso-electronic elements of silicon, in other words the elements of column IV of the periodic table of the elements, tin (Sn) and germanium (Ge).
    The “partition coefficient” specific to a given species, noted “k” in the text, defines the ratio of the concentration of said species incorporated in the solid phase and the concentration in the liquid phase at the solid / liquid interface.
    It is up to the person skilled in the art to adjust the amount of tracer agent (s) used at the level of the silicon charge and / or of the seed or seeds according to the invention so as to allow their detection by the LIBS technique in the molten silicon bath.
    In particular, when the method of the invention is implemented for the detection of the fm of fusion, the amount of tracer agent is adjusted so that the content of said tracer agent in the molten silicon bath, when the front of fusion has reached the desired stop position, exceeds the detection threshold by LIBS of said tracer agent.
    The detection threshold by LIBS, specific to a given species, corresponds to the minimum value of concentration in the liquid from which it is possible to detect the presence of said species.
    The tracer agents used according to the invention, in particular of the n-type or p-type doping agents, or iso-electronic elements of silicon, preferably have a detection threshold by LIBS at least of the order of ppm. , in particular approximately 1 ppm by weight, preferably at least of the order of a tenth of ppm, in particular approximately 0.1 ppm by weight.
    In the case of the use of tracer agents of the metal element type, the detection threshold by LIBS can be at least of the order of ten ppm (in particular approximately 10 ppm by weight), preferably of 1 '' about 0.3 ppm by weight.
    Such a detection threshold by the LIBS technique authorizes the use of a quantity of tracer agent (s) which is not detrimental to the properties of the final ingot which incorporates at least in part the tracer agent (s) used.
    Typically, the amounts of tracer agent (s) used in the feed and / or the seeds are such that at the end of the melting process, the molten silicon bath comprises between 0.1 and 100 ppm by weight, in particular between 0.3 and 10 ppm by weight of tracer agent (s).
    According to a first embodiment, the one or more tracers are chosen from doping agents of n type or of p type of silicon having a low partition coefficient, in particular a partition coefficient less than or equal to 10 ′ 1 .
    More particularly, the said tracer (s) according to the invention can be chosen from p-type doping agents with low partition coefficient, such as aluminum (Al), gallium (Ga), indium (In), and n-type doping agents with a low partition coefficient, such as antimony (Sb) and bismuth (Bi).
    Preferably, the tracing agents are chosen from Gallium, Indium and
    Antimony.
    Advantageously, such elements will be easily detectable by the LIBS technique in the molten silicon bath, while having little or no impact on the quality of the final ingot.
    In fact, as illustrated in Examples 2 and 3, the presence in the final ingot of said tracer (s) of n-type or p-type dopants can for example be compensated by adjusting the doping of type opposite to the tracer of the initial charge of silicon, so as to maintain the desired resistivity for the final silicon ingot.
    As an alternative, it is possible to take advantage of the use of one or more tracers of the n or p doping agent type according to the invention to obtain, at the end of the fusion, a molten silicon bath comprising the or said p-type and / or n-type doping tracer agents with an adequate content to lead to the doping and to the resistivity desired for the final ingot.
    For example, the use of a tracer of the p-doping agent type can advantageously make it possible to stabilize the resistivity of the final ingot in the context of the implementation of a so-called “compensated” silicon charge comprising both agents p-type and n-type dopants (typically boron / phosphorus), for example of metallurgical silicon type.
    The target resistivity value is chosen according to the applications envisaged for the silicon ingot, for example between 0.5 Q.cm and 10 Q.cm for the manufacture of photovoltaic cells.
    Typically, the amount of tracer (s) of doping agent (s) type n or p type, used according to the invention, is such that the content of tracers in the molten silicon bath, at the outcome of the stop of the fusion is between 0.1 and 100 ppm by weight (also noted “ppmw”), in particular between 0.3 and 10 ppm by weight.
    According to another particular embodiment, the one or more tracers are chosen from metal elements having a partition coefficient in silicon less than or equal to 10 ′ 4 , preferably less than or equal to 10 ′ 5 .
    In the case of the implementation, for example at the initial charge of silicon, of a tracer of the metallic element type in the form of pure material, said metallic element is more particularly chosen from elements having a higher melting temperature or equal to 1414 ° C.
    Such a criterion is not essential in the case of the use of a tracer of the metallic element type in the form of silicon doped with said tracer.
    In particular, the tracer can be chosen from tantalum (Ta), zirconium (Zr), osmium (Os), scandium (Sc), ruthenium (Ru), molybdenum (Mo), Niobium (Nb ), nickel (Ni), tungsten (W) and their mixtures.
    Preferably, the tracer is tungsten.
    Preferably, as mentioned above, the metal elements used as tracers advantageously have a detection threshold by the LIBS technique at least of the order of ten ppm (in particular about 10 ppm by weight), preferably of the order of 0.3 ppm by weight.
    ίο
    Advantageously, the quantity of tracers of the metallic element type used according to the invention is such that the content of tracers in the molten silicon bath, at the end of the melting stop, is as low as possible. authorizing its detection by LIBS.
    Thus, the quantity of tracer (s) incorporated in the filler and / or in the silicon seeds is such that the content in the molten silicon bath at the end of the fusion stop is slightly higher than the detection threshold of said tracer agent using the LIBS technique.
    As illustrated in Example 4 which follows, the addition of such a tracer to the image of tungsten has little or no impact on the final ingot. In fact, due to the very low partition coefficient of the metal element used as a tracer, the tracer very well segregated during the crystallization of the silicon ingot, only the last solidified fraction, subsequently removed by cutting from the top ingot, being enriched in tracer.
    This segregation phenomenon is well known and conventionally implemented in purification techniques by directed solidification of metallurgical silicon charges.
    Thus, the final ingot does not include, or only in the form of traces, the tracer of the metallic element type used.
    According to yet another particular embodiment, it is possible to choose the tracers from the elements of column IV of the periodic table, specifically germanium (Ge) and tin (Sn).
    These elements, iso-electronic of silicon, will advantageously have little or no influence on the electronic quality of the final ingot.
    Preferably, the tracer agent is chosen from germanium (Ge) and tin (Sn).
    Typically, the quantity of tracers of the isoelectronic element type of silicon, used according to the invention, is such that the content of tracers in the molten silicon bath, at the end of the melting stop, is between 0.1 and 100 ppm by weight, in particular between 0.3 and 10 ppm by weight.
    Preferably, the tracer agents used according to the invention are chosen from gallium, indium, antimony; tungsten; germanium and tin.
    In particular, the tracing agents used according to the invention are chosen from gallium, indium, tungsten, germanium and tin.
    Of course, it is possible to use several tracer agents according to the invention, in particular when they are positioned both at the level of the seeds and of the silicon charge, or even in different given positions of the silicon charge. .
    Positioning of tracer agents
    According to a first variant of the process of the invention, the tracer is incorporated at the level of said silicon seed (s).
    Such an alternative embodiment is illustrated in Example 1 (germs doped with germanium) and Example 2 (germs doped with gallium) which follow.
    The process of the invention advantageously makes it possible to identify the arrival of the melting front at the level of the germs.
    The incorporation of the tracer (s) at the level of one or more seeds is thus particularly suitable for detecting the end of fusion of the ingot production cycle, in other words the position of the melting front desired for stopping the program. melting furnace.
    In fact, as mentioned above, it is desirable, during the solidification directed by taking up on germs, to control the thickness of molten germ (s), before initiating the solidification of the silicon.
    The thickness of the seeds means the thickness of the seeds along the longitudinal axis (Z) of the crucible.
    The longitudinal axis (Z) of the crucible designates the line joining all of the barycenters of the cross sections of said crucible (walls of the crucible included). The longitudinal axis may more particularly be an axis of symmetry for the crucible.
    For example, it may be advantageous to melt only the said seed (s) to a given thickness, thereby eliminating the defects of the upper part of the seeds.
    In the context of the process of the invention, when the melting front reaches the said seed or seeds incorporating at least one tracer, the partial melting of the seed or seeds generates the presence in the molten silicon bath of the tracer. The LIBS technique makes it possible to assess the presence, and more precisely the content, of the tracers present in the liquid bath.
    It is thus possible to identify the moment when the melting front reaches the said germ (s), and more precisely to deduce, via quantification by LIBS analysis of the tracer agent (s), the molten thickness of the germ (s).
    Advantageously, the fusion process can be stopped (manually or automatically) at the desired position of the melting front, when the presence, or even a given quantity, of tracers is detected by measurement by LIBS in the silicon bath. fondue.
    According to another alternative embodiment of the method of the invention, the said tracer (s) can be incorporated in one or more positions given to the initial charge of silicon.
    The preparation of the silicon filler used according to the invention falls within the general knowledge of a person skilled in the art. It can consist of silicon in various forms, for example silicon pebbles, silicon microbeads, silicon wafers, optionally doped with n and / or p type, usually used for the directed solidification of a silicon ingot
    The silicon filler may in particular comprise, in addition to possibly one or more tracers according to the invention, one or more p-type and / or n-type doping agents conventionally used to obtain the desired doping for the silicon ingot.
    The tracer can be integrated into the initial charge of silicon, in the form of pure material or of silicon doped with said tracer. It can be in various forms, for example in the form of powders, beads, threads and / or platelets.
    Preferably, the tracers introduced according to the invention have a high purity to avoid any undesirable contamination of the silicon.
    Different positioning variants of said tracer or tracers at the silicon charge are conceivable, in particular with regard to information on the progress of the fusion which one wishes to take advantage of to optimize the directed solidification cycle.
    In the remainder of the text, the position of a tracer in the silicon charge is more particularly identified with respect to the distance (also designated as the height) of the tracer from the bottom of the crucible, measured along the axis (Z) longitudinal of the crucible.
    Thus, one or more tracer agents can be incorporated into the silicon charge at one or more predefined heights relative to the bottom of the crucible, measured along the longitudinal axis (Z) of the crucible.
    According to a particular embodiment, as illustrated in Examples 3 and 4 which follow, the position of the tracer is adjusted so as to correspond to the position of the melting front at which the melting program of the directed solidification furnace must be stopped.
    Determining the position of the melting front at which the furnace melting program must be stopped is within the competence of a person skilled in the art with regard to the furnace / recipe employed, and in particular taking into account the inertia of fusion (which translates the displacement of the melting front when changing the melting instructions towards solidification), for the effective stopping of the melting front at the desired height (in other words for a desired thickness of molten seeds).
    Thus, the position of the melting front at which the melting program of the directed solidification furnace must be stopped can be predetermined with regard to the desired thickness of molten seeds and the inertia of fusion.
    For example, the inertia of fusion can be evaluated during a prior directed solidification test, implementing the same oven control recipe.
    Without wishing to be bound by theory, as shown in FIG. 4, the tracer can thus be positioned at a height H T of the crucible bottom corresponding to the desired stopping height ("S") of the melting front to which is added merger inertia ("If").
    In a similar way to the case of the implementation of the tracer at the level of germs, it is thus possible to stop (manually or automatically) the melting process at the desired position of the melting front, when the presence or even a quantity given, in tracers is detected by the measurement by the LIBS technique in the molten silicon bath.
    According to yet another particular embodiment, tracers, of the same nature or of a different nature, may be present in several given positions of the silicon charge.
    The assessment of the presence (in the case of the use of different tracers), and / or the quantification (in the case of tracers of the same kind) by the LIBS technique of the tracers in the molten silicon bath during the melting of the charge makes it possible to deduce for example the melting speed (speed of progression of the melting front).
    According to yet another particular embodiment, one or more tracers can be present in one or more positions given in the silicon charge, in particular in the upper part of the silicon charge.
    The assessment by the LIBS technique of the content of tracer agents in the silicon bath makes it possible to deduce, with knowledge of the quantity of tracers initially introduced into the charge, the change in the volume of the molten bath during fusion, and therefore indirectly the progress of the merger.
    It is still possible, from knowledge of the progress of the fusion, to optimize the fusion process during the production cycle by directed solidification of the silicon ingot.
    For example, a tracer can be incorporated into the silicon charge, at a height H T ′ slightly greater than the height H T corresponding to the position of the melting front at which the melting program must be stopped.
    Therefore, the detection during the fusion of the presence of the tracer in the molten bath by the LIBS technique announces that the position for stopping the fusion process is soon reached. It may then be advantageous, during the detection by LIBS of the presence of the tracer agent in the molten bath, to reduce the rate of melting, in order to minimize the consumption of germs.
    It is understood that the different variants and embodiments described above can be combined.
    In particular, tracers, in particular of different natures, can be incorporated both at the level of the silicon charge, and at the level of said seed or seeds.
    Of course, the invention is not limited to the particular embodiments mentioned above. Various modifications can be made by a person skilled in the art, in particular with a view to accessing the desired information on the evolution of the melting front during the ingot preparation process by taking up on germs.
    LIBS measurement
    As mentioned above, the invention takes advantage of the spectroscopy technique on a laser-induced plasma, better known under the abbreviation "LIBS", to allow detection, and even quantification of the tracer (s), in particular as described previously, in the liquid silicon bath.
    The LIBS technique can for example be implemented using a device as proposed in documents WO 2004/001394 and WO 2015/177223 and particularly suitable for the online analysis by LIBS of a silicon bath molten.
    Conventionally, the means of analysis by LIBS technique can comprise a laser capable of generating a laser pulse towards the surface to be analyzed of said molten silicon bath, a set of mirrors allowing the focusing of the laser pulse towards the surface to be analyzed. , a telescope connected to an optical fiber allowing the collection of the emissions of the micro-plasma formed by the laser pulse, and an emission spectrometer allowing the analysis of the collected emissions.
    The measurement by LIBS can be carried out via an optical access or via a blowing rod of an inert gas, typically of argon, positioned on the surface of the molten bath.
    The blowing of inert gas makes it possible to avoid possible contamination of the surface to be analyzed of the molten silicon bath. Blowing inert gas can also have the advantage of increasing the detection limits of LIBS analysis.
    The LIBS measurement can be integrated into the standard argon flow Ar (l) typically used in solidification devices directed by germ recovery, or via an additional argon rod Ar (2), as shown in Figure 1 .
    The measurement device can also comprise means for rotary mechanical stirring of the liquid bath, as described in document WO 2015/177223, to promote the stabilization of the surface to be analyzed of the molten bath.
    According to yet another alternative embodiment, the measurement equipment by LIBS can be mobile to follow the progress of the melting for several furnaces in an industrial production configuration.
    It is understood that the measurement by LIBS is initiated after a given period of time to allow the establishment of a liquid silicon (or molten) phase at the surface of the silicon charge in the crucible. This period of time can be estimated by knowing the piloting recipe for the directed solidification furnace used, or even identified by pyrometric measurement.
    Preferably, the measurement in step (ii) by the LIBS technique of the composition of the molten bath can be carried out continuously. Due to the speed of data acquisition by the LIBS technique, it is possible to follow in real time the evolution of the chemical composition of the liquid bath, and in particular to continuously monitor the presence or the content of tracers in the bath. of silicon during fusion.
    The process may include the display of a signal, for example calibrated in ppm by weight as illustrated in FIG. 2, representative of the evolution of the content of tracer (s) in the molten bath during the melting.
    As mentioned above, the method of the invention proves to be particularly useful for detecting the end of melting, in other words for identifying the moment when the melting program of the oven must be stopped.
    Stopping the melting process and triggering the crystallization of the ingot can be carried out in manual or automated mode, based on the information obtained by the LIBS technique.
    Advantageously, the method of the invention makes it possible to automate the end of fusion of the ingot production cycle, in other words to program the automatic stopping of the fusion program.
    More specifically, the stopping of the melting program of the elaboration cycle by directed solidification can be programmed when the measurement by LIBS reaches a predefined limit, corresponding to the detection of a given quantity of tracer (s) in the molten bath.
    This limit value of melting fm can be predetermined by the skilled person, in consideration of the positioning and the quantity of tracers used and the parameters of the recipe / oven used, reproducible from a solidification cycle directed at the 'other (such as the inertia of fusion), as illustrated in the examples which follow.
    The use of the process of the invention advantageously makes it possible to optimize the process for preparing ingots by taking up germs, in particular in that it makes it possible to minimize the consumption of the germ (s) used. This is particularly advantageous in the context of germ recycling.
    Of course, the invention is not limited to the variant embodiments described above.
    The invention will now be described by means of the following examples and figures, given by way of non-limiting illustration of the invention.
    Figures
    Figure 1: Schematic representation, in cross section, of the directed solidification device implemented in Example 1;
    Figure 2: Schematic representation of the LIBS signal calibrated in ppm (by weight) associated with segments 6, 7, 8 and 9 of the control recipe for the directed solidification furnace according to Example 1;
    Figure 3: Simulation of the resistivity variations of the silicon ingot as a function of the solidified fraction, in the case of an ML-Si ingot with boron doping (Figure 3 (a)) and in the case of an ML ligot -If with doping with boron and doping with gallium (resulting from doping of germs with Ga) according to Example 2;
    Figure 4 Schematic representation, in cross section, of the positioning of antimony T tracers in the silicon charge (12) according to Example 3; and
    Figure 5 Schematic representation, in cross section, of the positioning of the tracers Tl, T2, T3, T4 and T5 of tungsten in the silicon charge (12) according to Example 4.
    It should be noted that, for reasons of clarity, the various elements in FIGS. 1, 4 and 5 are shown in free scale, the actual dimensions of the different parts not being observed.
    EXAMPLES
    The following examples are models for adapting the recipes for piloting cycles for the production of silicon ingots in a directed solidification furnace, in particular for the automation of the fusion / crystallization transition, from data obtained by the LIBS technique. according to the invention.
    These examples do not take into account the time for the homogenization of the tracer in the molten bath. This characteristic homogenization time can be integrated into the postulated experimental fusion inertia, reproducible from one cycle to another.
    EXAMPLE 1
    Automation of the end of fusion using germs doped with germanium
    Solidification device directed by recovery on germs
    The directed solidification device used is described with reference to FIG. 1.
    4.536 kg of seeds (11) of silicon Cz doped at 1.10 18 cm 3 with germanium (k Ge = 0.33) in the form of 4 seeds (dimensions: 15.6 x 15.6 x 2 cm 3 ). These germs are deposited at the bottom of a crucible (10), juxtaposed in the center.
    55,464 kg of high purity silicon filler (> 9 N) are positioned on these seeds in the crucible.
    Boron doping is provided by the addition of 34.7 g of silicon wafers deposited at about 2/3 of the height of the charge and doped with boron at a concentration of 1.62 × 10 19 cm 3 .
    The furnace used (33) is a conventional furnace for the directed solidification of silicon, allowing temperature controls with heating elements (top (31) and bottom (32)) and a partial pressure of argon.
    The triggering of the LIBS measurement is controlled by the oven after a segment time, or associated with the presence of liquid by pyrometric measurement.
    The LIBS measurement is carried out via an argon blowing rod (22) positioned on the surface of the molten bath. The LIBS analysis device (41) can for example be as described in document WO 2015/177223.
    The LIBS signal is sent to the oven controller.
    Unlike a conventional sprout recovery, there is no need to take an initial reference of the position of the surface of the sprouts relative to a reference frame by probing on the surface of the sprouts (zero coast used for the reference when the management is carried out by probing rod during fusion).
    Management of the fusion / crystallization transition
    The sequence of the silicon melting / crystallization cycle by taking up on seeds is as follows:
    - The stages of placing the oven under vacuum, initial heating up to the argon reentry temperature (600 mbar) and heating up to the silicon melting temperature are unchanged compared to a conventional solidification process directed.
    - The following table 1 provides the set values from the melting stage. The instructions for the melting level (segment 6) are unchanged.
    On the other hand, the melting stage is now associated with a special “end of fusion” function. The special “end of fusion” function records a real-time value from the LIBS measurement.
    The LIBS signal is proportional to the amount of germanium detected in the liquid bath. It can for example be calibrated in ppm by weight (ppmw) as illustrated in FIG. 2, or remain without unit.
    To allow the operator to check the validity of the measurement on the man / machine interface of the oven, it is for example possible to view the evolution of the LIBS signal as a function of time.
    - The "end of fusion" function generates the operator call for validation of the end of fusion. The end of fusion generates the transition from segment 6 to segment 7. If the operator does not validate within 3 minutes, the transition from segment 6 to segment 7 is automatic.
    After 408 minutes of segment 6, the preset threshold corresponding to 1 ppmw of Ge in the liquid is reached. The operator waits 2 minutes for confirmation of a signal above the threshold and validates the fusion fm 410 minutes after the start of segment 6 (Figure 2), for example by pressing the "OK" function of the interface message man / machine.
    This moment is rated "in tf merge" in Figure 2. At this stage, the merger of germs began.
    The LIBS signal is at 1 ppmw, which makes it possible to deduce that a portion close to 20% of the germs has melted at the time tf in fusion, or on average a melted thickness of the germs of 4 mm.
    During the course of segment 7, the fusion continues until the beginning of segment 8. This time is called Growth in FIG. 2.
    At this stage, the fusion of germs has stopped.
    The LIBS signal is maximum around 2.2 ppmw, which indicates that a portion close to 45% of the germs has melted at the Growth time, ie on average a melted thickness of 9 mm. The inertia of fusion, defined as the displacement of the solid / liquid interface between Cm of fusion and Growth, is therefore 5 mm. After a phase in which neither fusion nor growth is observed (fm of segment 8), solidification (segment 9) is initiated.
    No.segment Description Rampor landing Instructionsceiling(° C) Instructionssole (° C) Time(min) Functionspecial 6 Landingfusion Bearing 1500 1400 600 End of mergerLIBS 7 Transition 1 Ramp 1445 1200 60 8 Transition 2 Ramp 1445 1000 60 9 Solidification Ramp 1444 980 70
    Table 1: Example of a (non-exhaustive) recipe for the oven for the fusion / crystallization transition
    Result
    By the LIBS measurement associated with the addition of germanium in the germs, the recovery on germs can thus be automated.
    The use of germanium as a tracer agent at the level of germs has no impact in terms of quality (lifetime of the charge carriers), resistivity, and chemical properties, except for the presence of approximately 10 16 at.cm ' 3 of germanium in the resulting ingot.
    EXAMPLE 2
    Automation of the end of fusion using gallium doped germs
    Solidification device directed by recovery on germ
    42.5 kg of germs recycled from a Cz ingot of mono-like silicon (ML) are placed as in Example 1 at the bottom of the crucible, that is to say in the form of 25 germs of dimensions 15.6 x 15.6 x 3 cm 3 , i.e. in the form of a complete recycled paving 78 x 78 x 3 cm 3 .
    The Cz germs, initially 30 mm thick, are doped at 7.10 18 cm 3 in gallium.
    410 kg of high purity silicon filler (> 9 N) are positioned on these germs in the crucible.
    Boron doping is provided by the addition of 31 mg of pure boron powder in the middle of the silicon charge.
    The oven used is of capacity G5. It has three heating zones (ceiling, side, floor). The LIBS measurement was integrated as in Example 1 above the corner of the ingot 100 mm from the edges of the crucible.
    Management of the fusion / crystallization transition
    The sequence of the silicon melting / crystallization cycle by taking up on seeds is as follows:
    - The stages of placing the oven under vacuum, initial heating up to the argon reentry temperature (600 mbar) and heating up to the silicon melting temperature are unchanged compared to a conventional solidification process directed.
    - The special "end of fusion" function is activated for the melting stage. Five hours after the start of fusion, the LIBS measurement is launched (time corresponds to the establishment of the liquid on the surface of the molten charge).
    When 1 mm of residual Cz germ is melted over the entire surface, approximately 1.4 kg of Ga doped germ are mixed with the liquid silicon, generating a contamination of approximately 1.2 ppmw of the liquid bath. This contamination significantly above the detection limit generates the operator call which validates the jump to the next segment and therefore the end of the automated fusion.
    The inertia of fusion on this furnace / process has been optimized to be 3 mm. As a result, 4 mm of Cz germs contaminated Ga are homogeneously melted over the entire surface (i.e. 5.7 kg), and the contamination of the bath before the start of growth is of the order of 4.7 ppmw.
    Result
    By LIBS measurement associated with the addition of gallium in the germs, the recovery on germs can be automated.
    The consumption of germs is reduced. The LIBS technique allows rapid detection and good reproducibility with a small amount of molten germs (in this case, 4 mm of germs are consumed per automated cycle). The number of germ recycles can thus be greater.
    The residual gallium concentration in the final ingot obtained after directed solidification of the molten silicon charge mainly impacts the resistivity of the top of the ingot, as represented in FIG. 3 (b), compared to an ingot obtained only with doping with boron (FIG. 3 (a)).
    It is possible to minimize this impact by choosing a tracer agent having a lower partition coefficient k (for example In, Sb) or a non-doping tracer agent (for example Ge, Sn).
    Alternatively, it is possible to use gallium as a tracer agent in the case of a directed solidification of a boron / phosphorus compensated material of metallurgical silicon type, the presence of gallium (p-type doping agent) in the final ingot then serving to obtain the desired resistivity.
    EXAMPLE 3
    Automation of the end of fusion using a tracer agent (antimony) positioned at the level of the silicon charge
    Solidification device directed by recovery on germ
    The device is described with reference to FIG. 4.
    450 kg of silicon (12) high purity filler (> 9 N) are positioned in a crucible (10). The bottom of the filler (fine-grained polycrystalline silicon resulting from the production of silicon by the Siemens process) serves as a polycrystalline seed (11).
    Boron doping is provided by the addition of 37 mg of pure boron powder in the middle of the silicon charge.
    The inertia of fusion (If), associated with the couple oven / recipe (displacement of the solid / liquid interface between tfmde fusion and t C roissance) is 12 mm (this inertia can for example be determined by a first experiment of this type and experimental measurement of residual germ thickness).
    The tracer is made up of four basic plates 156 x 156 mm 2 and a thickness of 1.125 mm of silicon doped with 1.10 19 cm 3 of antimony.
    The desired stop edge of the melting front (“s” in FIG. 4) being 5 mm above the crucible bottom in the center of the ingot, the inertia of fusion If being 12 mm, the four plates “tracer »Are juxtaposed in the center at H T = 17 mm from the bottom of the crucible, as shown diagrammatically in section view in FIG. 4.
    The oven used is of capacity G5. It has a heating zone (ceiling). The LIBS measurement was integrated into the standard argon flow Ar (l) (shown in Figure 1), replacing the conventional probing device.
    Management of the fusion / crystallization transition
    The sequence of the silicon melting / crystallization cycle by taking up on seeds is as follows:
    - The stages of vacuuming the oven, initial heating up to the return temperature of argon (600 mbar) and heating to the melting temperature are unchanged compared to a conventional directed solidification process.
    - The special "end of fusion" function is activated for the melting stage. Five hours after the start of fusion, the LIBS measurement is started (time corresponding to the establishment of the liquid on the surface of the molten charge).
    The detection> noise level option is activated in the special function for rapid detection.
    - When the melting front reaches and exceeds the antimony tracer, the liquid bath is doped with 0.53 ppmw of Sb following the fusion of the 255 g of tracer.
    This contamination significantly higher than the LIBS detection limit of 0.4 ppmw generates the operator call which validates the jump to the next segment and therefore the end of the automated fusion as in Example 2.
    Result
    By LIBS measurement associated with the addition of antimony at the level of the silicon charge, the recovery on germs can be automated.
    Boron doping (p-type dopant), which is 0.075 mg / kg for solidification of an ingot without the addition of antimony, has been slightly increased to 0.09 mg / kg to take account of the presence of Sb , n-type doping agent, in the final ingot, in order to maintain the specification of the resistivity of the ingot from 1 to 2 Q.cm p-type of the example.
    In the case of the production of an n-type ingot, the content of antimony tracer could be adapted to generate the desired n-type ingot.
    The same example with the same concentration of tracer agent of the Ga or Ge type would not require any adjustment.
    EXAMPLE 4
    Automation of the end of fusion with the aid of a tracer agent (tungsten) positioned at the level of the silicon charge
    Solidification device directed by recovery on germ
    The device is described with reference to FIG. 5.
    800 kg of silicon (12) high purity filler (> 9 N) are positioned in the crucible (10). The bottom of the filler (fine-grained polycrystalline silicon resulting from the production of silicon by the Siemens process) serves as a polycrystalline seed (11).
    Boron doping is added by adding 60 mg of pure boron powder to the middle of the silicon charge.
    tracers (Tl, T2, T3, T4 and T5) made of pure tungsten (W) in the form of wire are arranged at different heights from the bottom of the crucible, separated vertically by spacers (El, E2, E3, E4 and E5), allowing the positioning of the tracers to be controlled above the seeds (11) at the bottom of the crucible, as shown diagrammatically, in section view, in FIG. 5.
    In the example, the tracers Tl, T2 and T3 are pieces of wire of 0.32 g and the tracers T4 and T5 are pieces of wire of 0.16 g.
    The spacers El, E2, E3 and E4 are 1 cm thick and consist of slices of ingots previously formed (recycled scrap). The thickness of the spacer E5 is 4 mm to adjust a consumption of germs under the tracer T5 of 2 mm due to a fusion inertia of 6 mm.
    The oven used is of capacity G6. It has a heating zone (ceiling). The LIBS measurement was integrated into the standard argon flow Ar (l) to replace the conventional probing device. A heat extractor with 4 opening positions (Off = closed; On-1, On-2 and On-3) generates an extraction of heat flow down the oven.
    Management of the fusion / crystallization transition
    The sequence of the silicon melting / crystallization cycle by taking up on seeds is as follows:
    - The stages of vacuuming the oven, initial heating up to the return temperature of argon (600 mbar) and heating to the melting temperature are unchanged compared to a conventional directed solidification process.
    - The special "end of fusion" function is activated for the melting stage. Five hours after the start of fusion, the LIBS measurement is started (time corresponding to the establishment of the liquid on the surface of the molten charge).
    The detection> noise level option is activated in the special function for rapid detection.
    - When the melting front reaches and exceeds respectively the tracers 1, 2, 3, 4 and 5, the liquid bath is gradually doped at 0.4 ppmw; 0.8 ppmw; 1.2 ppmw; 1.4 ppmw and 1.6 ppmw. This contamination makes it possible to monitor the melting front and to deduce the melting speed. The tracer 5 triggers the segment jump from segment 6 to segment 7 of the oven recipe summarized in Table 2 below, by exceeding the LIBS threshold at 1.5 ppmw.
    No.segment Description Ramporbearing Instructionsceiling(° C) Extractionheat Time(min) Functionspecial 6 Landingfusion Bearing 1550 Off 600 End of mergerLIBS 7 Transition 1 Ramp 1475 On-1 60 8 Transition 2 Ramp 1445 On-2 60 9 Solidification Ramp 1444 On-3 70
    Table 2: Example of a (non-exhaustive) recipe for the oven for the fusion / crystallization transition
    Result
    By LIBS measurement associated with the addition of tungsten at the level of the silicon charge, the recovery on germs can be automated.
    Adding tungsten to the silicon charge has no impact on the final ingot. Due to the very low partition coefficient of tungsten in silicon (2.10 ' 8 ), the tungsten segregated very well, only the last solidified fraction, eliminated by cutting the ingot, is enriched in tungsten.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    1. A useful method for monitoring the progress of the fusion during the preparation of a silicon ingot by solidification directed by recovery on seeds, comprising at least the steps consisting of:
    (i) have, in a crucible, a silicon charge positioned on the surface of one or more silicon nuclei;
    said seed (s), and / or said silicon charge in one or more given position (s), comprising one or more elements, called tracer agents, chosen from:
    . n-type or p-type doping agents having a partition coefficient in silicon less than or equal to 10 ′ 1 ;
    . the metallic elements having a partition coefficient in silicon less than or equal to 10 '4; and. the elements, iso-electronic of silicon, germanium (Ge) and tin (Sn);
    (ii) assess, during the melting of the silicon charge, the presence and / or the quantity of tracer agent (s) by a chemical measurement technique of laser-induced plasma spectroscopy (LIBS) type the surface of the molten silicon bath; and (iii) determine, from the LIBS measure (s), the progress of the merger.
    [2" id="c-fr-0002]
    2. Method according to the preceding claim, in which the said tracer agent or agents are chosen from p-type doping agents with a partition coefficient in silicon less than or equal to 10 ′ 1 , in particular aluminum, gallium, l indium; and n-type doping agents with a partition coefficient in silicon less than or equal to 10 ′ 1 , in particular antimony and bismuth, preferably said tracer (s) are chosen from Ga, In and Sb.
    [3" id="c-fr-0003]
    3. Method according to any one of the preceding claims, in which the one or more tracer agents are chosen from metal elements having a partition coefficient in silicon less than or equal to 10 ' 4 , in particular less than or equal to 10' 5 , and having, in the case of the use of said tracer or agents of the metallic element type in the form of pure material, a melting temperature greater than or equal to 1414 ° C.
    [4" id="c-fr-0004]
    4. Method according to the preceding claim, wherein the said tracer agent (s) are chosen from tantalum (Ta), zirconium (Zr), osmium (Os), scandium (Sc), ruthenium (Ru), molybdenum (Mo), Niobium (Nb), nickel (Ni) and tungsten (W), preferably tungsten (W).
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, in which the one or more tracing agents are chosen from germanium (Ge) and tin (Sn).
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, in which the one or more tracing agents are chosen from gallium, indium, tungsten, germanium and tin.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, in which the said tracer agent (s) are present at the level of the said silicon nucleus (s), the said method being more particularly useful for detecting the end of fusion of the ingot processing cycle.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, in which the one or more tracer agents are incorporated into the silicon charge at one or more predefined heights relative to the bottom of the crucible, measured according to the longitudinal (Z) tax of the crucible.
    [9" id="c-fr-0009]
    9. Method according to the preceding claim, in which the tracer agent (s) are incorporated into the silicon filler in the form of pure material or of silicon doped with the tracer (s), in particular in the form of powder, beads, wires and / or platelets.
    [10" id="c-fr-0010]
    10. The method of claim 8 or 9, wherein the position of at least one tracer is adjusted to correspond to the position of the melting front at which the melting program of the directed solidification furnace is to be stopped.
    [11" id="c-fr-0011]
    11. Method according to the preceding claim, wherein the position of the melting front at which the melting program of the directed solidification furnace must be stopped is predetermined with regard to the desired thickness of molten seeds and the inertia of fusion.
    [12" id="c-fr-0012]
    12. Method according to any one of the preceding claims, in which the measurement by LIBS is carried out via an optical access or via a blowing rod of an inert gas, in particular of argon, positioned on the surface of the molten bath.
    [13" id="c-fr-0013]
    13. Method according to any one of the preceding claims, in which the measurement in step (ii) by LIBS is carried out continuously.
    [14" id="c-fr-0014]
    14. Method according to the preceding claim, comprising the display of a signal, for example calibrated in ppm by weight, representative of the evolution of the content of
    5 tracer (s) in the molten silicon bath during fusion.
    [15" id="c-fr-0015]
    15. Use of a method as defined according to any one of the preceding claims, for the detection of the fm of fusion of a cycle for the production of an ingot by solidification directed by recovery on germs, in particular for automating termination of the melting program for the directed solidification furnace.
    10
    [0016]
    16. Use according to the preceding claim, comprising stopping the fusion program when the measurement by LIBS reaches a predefined limit, corresponding to the detection of a given quantity of tracer (s) in the molten bath.
    1/3
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    同族专利:
    公开号 | 公开日
    EP3323912A1|2018-05-23|
    FR3059013B1|2019-03-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2005289770A|2004-04-02|2005-10-20|Canon Inc|Method for manufacturing crystal and crystal manufacturing apparatus|
    FR3021407A1|2014-05-23|2015-11-27|Commissariat Energie Atomique|DEVICE FOR ANALYZING OXIDABLE FUSION METAL BY LIBS TECHNIQUE|
    JP6935790B2|2018-10-15|2021-09-15|株式会社Sumco|Evaluation method of the inner peripheral surface of the quartz crucible and the evaluation device of the inner peripheral surface of the quartz crucible|
    CN109828083A|2018-12-26|2019-05-31|国联汽车动力电池研究院有限责任公司|High-temperature molten salt physicochemical properties test macro|
    CN112813495A|2019-11-18|2021-05-18|苏州阿特斯阳光电力科技有限公司|Method for recycling seed crystals for monocrystalline silicon-like ingot casting|
    CN113740314A|2021-08-05|2021-12-03|合肥金星机电科技发展有限公司|Full-automatic online detection method and system for high-temperature melt components|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1661209|2016-11-18|
    FR1661209A|FR3059013B1|2016-11-18|2016-11-18|MONITORING THE ADVANCEMENT OF LIBS-BASED FUSION DURING THE PRODUCTION OF A INGOT BY SOLIDIFICATION DIRECTED BY REPEAT ON GERMS|FR1661209A| FR3059013B1|2016-11-18|2016-11-18|MONITORING THE ADVANCEMENT OF LIBS-BASED FUSION DURING THE PRODUCTION OF A INGOT BY SOLIDIFICATION DIRECTED BY REPEAT ON GERMS|
    EP17201372.4A| EP3323912A1|2016-11-18|2017-11-13|Monitoring of the progress of melting by libs technique in the preparation of an ingot by directional solidification by seed recovery|
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